Hydrodesulfurization, deoxygenation and dewaxing processes with water stable catalysts for biomass-containing hydrocarbon feedstocks

ABSTRACT

This invention relates to a method for hydroprocessing feedstreams containing both sulfur-containing mineral oils and biomass-derived feedstocks in a single reactor configuration. The process produces a desulfurized, deoxygenated and dewaxed hydrocarbon product having reduced oxygen content, increased iso-paraffin content, low n-paraffin content, and good cold flow properties. In preferred embodiments, the processes herein utilize water tolerant hydrodewaxing catalysts in order to prevent deactivation and/or catalyst loss due to water produced during the deoxygenation reactions in the biomass components.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser.No. 61/655,217 filed Jun. 4, 2012, which is herein incorporated byreference in its entirety.

FIELD OF THE INVENTION

This invention relates to a method for processing feedstreams containingboth sulfur-containing mineral oils and biomass-derived feedstocks in asingle reactor configuration. The process produces a desulfurized,deoxygenated and dewaxed hydrocarbon product having reduced oxygencontent, increased iso-paraffin content, low n-paraffin content, andgood cold flow properties.

BACKGROUND

With decreasing availability of fossil carbon resources, there is anincreasing demand for alternative resources for use as hydrocarbon basedfuels and chemical base stocks. Biomass feedstocks present an enormouspotential in this respect, as they are renewable and can be CO₂ neutral.In contrast to crude oil (upon which “mineral oils” may be derived),however, biomass and biomass-derived materials typically contain largeconcentrations of oxygenates. In most cases, the oxygen atoms areremoved as water during deoxygenation processing, and, in some casessuch as pyrolysis oil, the feed already contains large amounts of water.

A problem that exists is that most existing refinery processes andassociated equipment are designed to process only crude oils or “mineraloil” based feedstocks. Processing of biomass derived feedstocks oftenrequires separate processing steps, equipment and catalysts forconverting these feedstocks into motor fuels and chemical feedstocks andsuch process may not be compatible with co-processing of theseconventional (mineral oil) feedstocks. The existing refinery systemsdesigned for processing strictly mineral based feedstocks are notdesigned with dedicated processes to handle both the biomass derivedfeedstocks and the conventional feedstocks separately. Costs to do sowould be prohibited.

Presently, there are many differing mandates in the different countriesrequiring a portion of the motor fuel pool be derived from biomasscomponents. However, most of these mandated percentages are small(typically from about 5 to 20% of the fuel composition to be based onbiomass/biofuels) with crude oils/mineral oils still making up the vastmajority of the fuel composition.

This is forcing conventionally crude processing refineries to invent newprocesses and catalysts for co-processing these mineral oil/biomassfeedstocks, which as discussed, can often be incompatible withconventional refinery equipment, processes and catalysts. A furtherrestrictive factor is that the economics are prohibitive for a refineryto invest significant additional capital dollars to add or considerablyalter the existing process equipment. This includes restrictions onsignificantly modifying existing process configurations that aredesigned to upgrade mineral oil based feedstocks into motor fuels,chemical feedstocks and other hydrocarbon products. Other restrictions,such as limited land space, may additionally prohibit the significantlymodification/addition of associated process equipment. A particularlyexpensive and prohibitive cost would be the need to add or replace ahigh pressure reactor associated with hydroprocessing of mineral oils inorder to separately upgrade such mixed feedstocks.

As noted prior, the processing of most biomass derived feedstocks, orthe portion there of which has been mixed with conventional feedstocks,requires the removal of oxygen that is inherently in the biomassfeedstocks. This has not been an issue addressed in conventionalrefining processes as most crude feedstocks do not contain appreciableamounts of oxygen.

Water is known to have a deactivating effect on many catalytic systemsused in conventional refinery-type processes. Catalysts containingalumina are known to be very sensitive to water, even at very lowconcentrations (in the parts per million range). Several prior artreferences describing catalyst compositions effective for deoxygenationalso note the necessity for maintaining low oxygenate concentrations inthe feedstocks.

For instance, the article by J. Hancsok et al. (Microporous andMesoporous Materials, 101 (2007), 148-152) describes a metal/zeolitecatalyst used for isomerizing oxygenate-containing feedstocks. Thecatalyst is bound with alumina, and it is noted that oxygenate contentsof just over 1% in the feedstock cause a 50% acidity loss, indicating areduced conversion activity. Additionally, the article by O. V.Kikhtyanin et al. (Fuel, 89 (2010), 3085-3092) describes a metal/SAPOcatalyst, also bound with alumina, which is used for hydroconversion ofsunflower oil. It was noted that fast deactivation was observed intandem with high oxygenate concentrations (relative to non-oxygenatedhydrocarbon concentrations), although the goal of the study was to findprocessing conditions that mitigated such issues.

Indeed, catalysts containing alumina can be among the most effectivecatalysts for many necessary processes, such as heteroatom removal(e.g., deoxygenation) and isomerization. Water-induced deactivation ofsuch catalysts can occur via numerous mechanisms (e.g., sintering,titration of acid sites, competitive adsorption, zeolite supportdealumination, and reduction of mechanical stability, inter alia), andsuch deactivation should be an increasingly important issue, due to theincreasing demand for biofuels and other biomass-derived products.

A significant problem that exists with the co-processing of feedstockscontaining a mixture of both mineral oils and biomass, is that there isstill a need to remove a significant amount of sulfur from the combinedfeedstock (which is typically associated with the mineral oil component)while simultaneously removing a significant amount of oxygen, andresultant water from the combined feedstock (which is typicallyassociated with the biomass component). As noted prior, achieving bothof these simultaneously in a given refinery process and catalyst systemhas resulted in less than adequate results mainly due to catalystinstability and/or significant losses in hydrodesulfurizationefficiencies in the catalyst system.

What is needed in the industry is a solution to this problem faced byrefineries to co-process feedstocks containing a mixture of both mineraloils and biomass while working within the constraints of existingequipment and processes to achieve fuel products that meet refineryspecifications such as biomass content, oxygen content, sulfur content,and cloud point.

SUMMARY OF PREFERRED EMBODIMENTS OF THE INVENTION

The embodiments of the invention herein are process & catalyst solutionsto enable existing mineral oil refineries to co-process feedstockscontaining a mixture of both mineral oils and biomass to achieve fuelproducts that meet refinery specifications such as biomass content,oxygen content, sulfur content, and cloud point while maximizing the useof existing refinery equipment.

In an embodiment is a method for processing a hydrocarbon feedstockcomprised of a mineral oil component and a biomass oil component to format least one liquid motor fuel product, such method comprising:

a) contacting the hydrocarbon feedstock and a first hydrogen treat gasstream with a hydrodesulfurization/deoxygenation catalyst in a firstreaction zone of a hydroprocessing reactor under first hydroprocessingconditions sufficient to produce a first reaction zone effluent whichcontains less organically bound sulfur than the hydrocarbon feedstockand less organically bound oxygen than the hydrocarbon feedstock;

b) contacting the first reaction zone effluent with a dewaxing catalystin a second reaction zone of the hydroprocessing reactor under secondhydroprocessing conditions sufficient to produce a second reaction zoneeffluent;

c) separating a gas phase product stream from the second reaction zoneeffluent to produce a reactor effluent product which has a lower sulfurcontent and a lower oxygen content than the hydrocarbon feedstock; and

d) producing at least one liquid motor fuel product from at least aportion of the reactor effluent product;

wherein the dewaxing catalyst comprises a zeolitic support, at least oneactive metal compound comprising one or more of Group VIB metals andGroup VIII metals deposited thereon, and a hydrophilic,hydrothermally-stable binder comprising one or more of: (A) an oxide,carbide, nitride, phosphide, sulfide, or combination thereof of one ormore metals selected from titanium, zirconium, vanadium, molybdenum,manganese, and cerium, (B) activated carbon, and (C) carbon on which isdeposited one or more metals selected from titanium, zirconium,vanadium, molybdenum, manganese, and cerium.

In preferred embodiments, the binder of the dewaxing catalyst compriseszirconia, vanadia, titania, molybdenum oxide, manganese oxide, ceriumoxide, carbon, or a combination thereof. Whereas in more preferredembodiments, the binder of the dewaxing catalyst comprises one or metalsselected from titanium, zirconium, vanadium, molybdenum, manganese, andcerium. While in most preferred embodiments, the binder of the dewaxingcatalyst comprises titanium.

In other preferred embodiments, the zeolitic support of the dewaxingcatalyst comprises ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-48, zeolite Beta,zeolite Y, USY, mordenite, ferrierite, or a combination thereof. Inother embodiments, the hydrodesulfurization/deoxygenation catalystcomprises at least one Group VIII metal oxide selected from Fe, Co andNi, and at least one Group VI metal oxide selected from Mo and W and asupport selected from alumina, silica, and silica-alumina.

In other preferred embodiments, at least one liquid motor fuel productis produced from a diesel boiling range fraction of the reactor effluentproduct wherein the cloud point of the diesel boiling range fraction isless than 0° C.

In preferred embodiments, the hydrocarbon feedstock contains from 80 wt% to about 98 wt % of the mineral oil component and from 2 wt % to about20 wt % of the biomass oil component, the mineral oil component containsat least 500 ppmw sulfur, and the reactor effluent product contains lessthan 100 ppmw sulfur. In other preferred embodiments, the secondhydroprocessing conditions include a water partial pressure of greaterthan 2 psia, greater than 5 psia, or even greater than 10 psia.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates a simplified of a process schematic of a firstembodiment of the hydroprocessing reactor system and associated productseparation systems of invention.

FIG. 2 illustrates a simplified process schematic of a second embodimentof the hydroprocessing reactor system and associated product separationsystems of invention.

FIG. 3 shows comparative GC-MS spectra of a stearic acid feed convertedusing two different catalyst compositions having identical metal andsupport components but differing in the binder component.

DETAILED DESCRIPTION OF THE EMBODIMENTS

The present invention relates to processes and catalysts for producing adesulfurized, deoxygenated, and dewaxed hydrocarbon motor fuel productstream from a hydrocarbon feedstock comprised of a mineral oil componentand a biomass oil component utilizing a two-part catalyst system in asingle hydroprocessing reactor. Preferably, an existing refineryhydroprocessing reactor can be utilized in the processes herein toeconomically retrofit an existing conventional (mineral oil) refiningprocess into a process for refining the hydrocarbon feedstock comprisedboth the mineral oil and biomass oil components.

Feedstock

The processes and catalysts of invention herein are designed to processmixed hydrocarbon feedstock comprised of both a mineral oil (or“conventional oil”) component and a biomass oil (or “biomass” or“biomass-derived” or “biofeed”) component.

In an embodiment, the hydrocarbon feedstock can have an initial boilingpoint of at least about 200° F. (93° C.), or at least about 250° F.(121° C.), or at least about 300° F. (149° C.), or at least about 350°F. (177° C.), or at least about 400° F. (204° C.), or at least about450° F. (232° C.). The initial boiling can vary widely, depending on howmuch kerosene or other lighter distillate components are included in afeedstock. In another embodiment, the hydrocarbon feedstock can have afinal boiling point of about 800° F. (427° C.) or less, or about 750° F.(399° C.) or less, or about 700° F. (371° C.) or less. Alternatively, inembodiments where fractionation is used to produce both a heavy dieselfraction and a separate bottoms fraction, the final boiling point can beabout 1100° F. (593° C.) or less, or about 1000° F. (538° C.) or less,or about 900° F. (482° C.) or less. Another way of characterizing afeedstock is based on the boiling point required to boil a specifiedpercentage of the feed. For example, the temperature required to boil atleast 5 wt % of a feed is referred to as a “T5” boiling point. Whencharacterizing a feed based on a T5 boiling point, the feedstock canhave a T5 boiling point at least about 200° F. (93° C.), or at leastabout 250° F. (121° C.), or at least about 300° F. (149° C.), or atleast about 350° F. (177° C.), or at least about 400° F. (204° C.), orat least about 450° F. (232° C.). In another embodiment, the feed canhave a T95 boiling point of about 800° F. (427° C.) or less, or about750° F. (399° C.) or less, or about 700° F. (371° C.) or less. Examplesof suitable feeds include various atmospheric and/or vacuum gas oilfeeds, diesel boiling range feeds, and feeds corresponding to mixturesthereof.

In one embodiment, the hydrocarbon feedstock can include at least 0.5 wt% biomass, based on total weight of the hydrocarbon feedstock provided,more preferably at least 1 wt %; for example at least 2 wt %, at least 3wt %, at least 4 wt %, at least 5 wt %, at least 10 wt %, at least 20 wt%, at least 30 wt %, at least 40 wt %, at least 50 wt %, at least 60 wt%, at least 70 wt %, at least 80 wt %, at least 90 wt %, at least 95 wt%, or at least 99 wt %.

Preferably, the biomass component is from about 2 wt % to about 20 wt %,or more preferably from about 5 wt % to about 15 wt %, of thehydrocarbon feedstock. In other preferred embodiments, the mineral oilcomponent is from about 80 wt % to about 98 wt %, or more preferablyfrom about 85 wt % to about 95 wt %, of the hydrocarbon feedstock.

Mineral Oil Component

The processes and catalysts of invention herein are designed to processmixed hydrocarbon feedstock comprised of both a mineral oil (or“conventional oil”) component and a biomass (or “biomass-derived”)component. The mineral oil component is the component that is derivedfrom “non-renewable” fossil/mineral oil reserves such as crude oils, tarsands bitumens, as well as liquid hydrocarbon streams derived from tarsands bitumen, coal, or oil shale. These are considered as“non-renewable” resources as the time frame required for production andreplacement of these supplies of mineral oils is at least severalthousands of years. Examples of mineral oils can include, but are notlimited to, straight run (atmospheric) gas oils, vacuum gas oils,demetallized oils, coker distillates, cat cracker distillates, heavynaphthas, diesel boiling range distillate fraction, jet fuel boilingrange distillate fraction, kerosene boiling range distillate fraction,and coal liquids. The mineral oil portion of the feedstocks herein cancomprise any one of these example streams or any combination thereof.

In preferred embodiments of the invention herein, the mineral oilcomponent contains at least 250 ppmw of sulfur. More preferably in theprocesses herein, the mineral oil component contains, at least 500 ppmw,or at least 1,000 ppmw, or at least 5,000 ppmw, or even at least 10,000ppmw sulfur. The majority of the sulfur present in the mineral oilcomponent will be organically bound sulfur.

Biomass Component

Generally, the biological materials that make up the biomass componentcan include vegetable fats/oils, animal fats/oils, fish oils, pyrolysisoils, and algae lipids/oils, as well as components of such materials. Insome embodiments, the biomass can include one or more type of lipidcompounds, which are typically biological compounds that are insolublein water, but soluble in nonpolar (or fat) solvents. Non-limitingexamples of such solvents include alcohols, ethers, chloroform, alkylacetates, benzene, and combinations thereof.

Major classes of lipids include, but are not necessarily limited to,fatty acids, glycerol-derived lipids (including fats, oils andphospholipids), sphingosine-derived lipids (including ceramides,cerebrosides, gangliosides, and sphingomyelins), steroids and theirderivatives, terpenes and their derivatives, fat-soluble vitamins,certain aromatic compounds, and long-chain alcohols and waxes.

In living organisms, lipids generally serve as the basis for cellmembranes and as a form of fuel storage. Lipids can also be foundconjugated with proteins or carbohydrates, such as in the form oflipoproteins and lipopolysaccharides.

Examples of vegetable oils that can be used in accordance with thisinvention include, but are not limited to rapeseed (canola) oil, soybeanoil, coconut oil, sunflower oil, palm oil, palm kernel oil, peanut oil,linseed oil, tall oil, corn oil, castor oil, jatropha oil, jojoba oil,olive oil, flaxseed oil, camelina oil, safflower oil, babassu oil,tallow oil and rice bran oil.

Vegetable oils as referred to herein can also include processedvegetable oil material. Non-limiting examples of processed vegetable oilmaterial include fatty acids and fatty acid alkyl esters. Alkyl esterstypically include C₁-C₅ alkyl esters. One or more of methyl, ethyl, andpropyl esters are preferred.

Examples of animal fats that can be used in accordance with theinvention include, but are not limited to, beef fat (tallow), hog fat(lard), turkey fat, fish fat/oil, and chicken fat. The animal fats canbe obtained from any suitable source including restaurants and meatproduction facilities.

Animal fats as referred to herein also include processed animal fatmaterial. Non-limiting examples of processed animal fat material includefatty acids and fatty acid alkyl esters. Alkyl esters typically includeC₁-C₅ alkyl esters. One or more of methyl, ethyl, and propyl esters arepreferred.

Algae oils or lipids are typically contained in algae in the form ofmembrane components, storage products, and metabolites. Certain algalstrains, particularly microalgae such as diatoms and cyanobacteria,contain proportionally high levels of lipids. Algal sources for thealgae oils can contain varying amounts, e.g., from 2 wt % to 40 wt % oflipids, based on total weight of the biomass itself. Additionally oralternately, algae can be genetically modified to produce oils that arenot lipids, e.g., that contain oxygenated hydrocarbons, such as waxesters, fatty ketones, fatty aldehydes, fatty alcohols, and the like.Further additionally or alternately, algae can be genetically modifiedto produce non-oxygenated hydrocarbons. In such cases, due to thegenetic modifications, the algae may indeed exhibit an increased contentof oil material and/or such oil material may advantageously have reducedoxygen content, compared to contents observable and/or attainable inconventional biomass.

Algal sources for algae oils include, but are not limited to,unicellular and multicellular algae. Examples of such algae can includea rhodophyte, chlorophyte, heterokontophyte, tribophyte, glaucophyte,chlorarachniophyte, euglenoid, haptophyte, cryptomonad, dinoflagellum,phytoplankton, and the like, and combinations thereof. In oneembodiment, algae can be of the classes Chlorophyceae and/or Haptophyta.Specific species can include, but are not limited to, Neochlorisoleoabundans, Scenedesmus dimorphus, Euglena gracilis, Phaeodactylumtricornutum, Pleurochrysis carterae, Prymnesium parvum, Tetraselmischui, and Chlamydomonas reinhardtii. Additional or alternate nonlimitingexamples of algae can include, but are not limited to, Achnanthes,Amphiprora, Amphora, Ankistrodesmus, Asteromonas, Boekelovia,Borodinella, Botryococcus, Bracteococcus, Chaetoceros, Carteria,Chlamydomonas, Chlorococcum, Chlorogonium, Chlorella, Chroomonas,Chrysosphaera, Cricosphaera, Crypthecodinium, Cryptomonas, Cyclotella,Dunaliella, Ellipsoidon, Emiliania, Eremosphaera, Ernodesmius, Euglena,Franceia, Fragilaria, Gloeothamnion, Haematococcus, Halocafeteria,Hymenomonas, Isochrysis, Lepocinclis, Micractinium, Monoraphidium,Nannochloris, Nannochloropsis, Navicula, Neochloris, Nephrochloris,Nephroselmis, Nitzschia, Ochromonas, Oedogonium, Oocystis, Ostreococcus,Pavlova, Parachlorella, Pascheria, Phaeodactylum, Phagus, Platymonas,Pleurochrysis, Pleurococcus, Prototheca, Pseudochlorella, Pyramimonas,Pyrobotrys, Scenedesmus, Schizochytrium, Skeletonema, Spyrogyra,Stichococcus, Tetraselmis, Thraustochytrium, Viridiella, and Volvoxspecies.

Other examples of prokaryotic organisms (whether wild-type orgenetically modified), which include cyanobacterial species, from whichoils qualifying as algae oils herein can be isolated/derived caninclude, but are not limited to, one or more of the following species:Agmenellum, Anabaena, Anabaenopsis, Anacystis, Aphanizomenon,Arthrospira, Asterocapsa, Borzia, Calothrix, Chamaesiphon,Chlorogloeopsis, Chroococcidiopsis, Chroococcus, Crinalium, Cyanobacterium, Cyanobium, Cyanocystis, Cyanospira, Cyanothece,Cylindrospermopsis, Cylindrospermum, Dactylococcopsis, Dermocarpella,Fischerella, Fremyella, Geitleria, Geitlerinema, Gloeobacter,Gloeocapsa, Gloeothece, Halospirulina, Iyengariella, Leptolyngbya,Limnothrix, Lyngbya, Microcoleus, Microcystis, Myxosarcina, Nodularia,Nostoc, Nostochopsis, Oscillatoria, Phormidium, Planktothrix,Pleurocapsa, Prochlorococcus, Prochloron, Prochlorothrix, Pseudanabaena,Rivularia, Schizothrix, Scytonema, Spirulina, Stanieria, Starria,Stigonema, Symploca, Synechococcus, Synechocystis, Tolypothrix,Trichodesmium, Tychonema, and Xenococcus.

In some embodiments the biomass component can comprise a fatty acidalkyl ester. In such embodiments, the fatty acid alkyl ester canpreferably comprise fatty acid methyl esters (FAME), fatty acid ethylesters (FAEE), and/or fatty acid propyl esters.

Additionally or alternately, the biomass component can include at leastabout 1 wt % oxygen, for example at least about 2 wt %, at least about 3wt %, at least about 4 wt %, at least about 5 wt %, at least about 6 wt%, or at least about 8 wt %. The majority of the oxygen present in thebiomass component will be organically bound oxygen.

Reactor/Processes/Catalysts

The processes of the present invention preferably utilize a singlereactor comprised of at least two catalyst beds with processes andcatalysts for producing a desulfurized, deoxygenated, and dewaxedhydrocarbon motor fuel product stream from a hydrocarbon feedstockcomprised of a mineral oil component and a biomass oil component.Preferably, by utilizing the processes and catalysts described herein,an existing refinery hydroprocessing reactor can be utilized toeconomically retrofit an existing conventional (mineral oil) refiningprocess into a process for refining the hydrocarbon feedstocks hereinwhich are comprised both the sulfur-containing mineral oil andoxygen-containing biomass oil components.

First Reaction Zone

In the processes herein, the first reaction zone contains a catalystoperated under first hydroprocessing conditions suitable for bothhydrodesulfurizing and deoxygenating the combined hydrocarbon feedstockcomprising both a mineral oil component and a biomass oil component.This first reaction zone may contain multiple catalyst beds. However, inthis zone, at least one of these catalysts beds is to be comprised ofthe “hydrodesulfurization/deoxygenation catalyst”, or as may bealternately referred to herein as the “first catalyst”, as furtherdescribed herein.

This first catalyst is preferably comprised of at least one Group VIIImetal oxide, preferably an oxide of a metal selected from Fe, Co and Ni,more preferably selected from Co and/or Ni, and most preferably Co; andat least one Group VI metal oxide, preferably an oxide of a metalselected from Mo and W, more preferably Mo, on a high surface areasupport material, preferably comprising alumina, silica, orsilica-alumina. Other suitable hydrodesulfurization/deoxygenationcatalysts include zeolitic catalysts, as well as noble metal catalystswhere the noble metal is selected from Pd and Pt. Preferably, the GroupVIII metal oxide of the hydrodesulfurization/deoxygenation catalyst ispresent in an amount ranging from about 0.1 to about 20 wt %, preferablyfrom about 1 to about 12 wt %, based on the weight of the catalyst. TheGroup VI metal oxide is preferably present in an amount ranging fromabout 1 to about 50 wt %, preferably from about 2 to about 20 wt %,based on the weight of the catalyst.

The hydrodesulfurization/deoxygenation catalysts used in the practice ofthe present invention are preferably supported catalysts. Any suitablerefractory catalyst support material, preferably inorganic oxide supportmaterials, can be used as supports for thehydrodesulfurization/deoxygenation catalyst utilized in the presentinvention. Non-limiting examples of suitable support materials include:zeolites, alumina, silica, titania, calcium oxide, strontium oxide,barium oxide, carbons, zirconia, diatomaceous earth, lanthanide oxidesincluding cerium oxide, lanthanum oxide, neodynium oxide, yttrium oxide,and praesodymium oxide; chromia, thorium oxide, urania, niobia, tantala,tin oxide, zinc oxide, and aluminum phosphate. Preferred are alumina,silica, and silica-alumina. More preferred is alumina.

Preferred conditions in this first reaction zone of the hydroprocessingreactor include contacting the hydrocarbon feedstock and a firsthydrogen treat gas stream with the hydrodesulfurization/deoxygenationcatalyst under first hydroprocessing conditions sufficient to produce afirst reaction zone effluent which contains less organically boundsulfur than the feedstock and less organically bound oxygen than thehydrocarbon feedstock.

These first hydroprocessing conditions can comprise one or more of: aweight average bed temperature (WABT) from about 500° F. (about 260° C.)to about 800° F. (about 427° C.), for example from about 550° F. (about288° C.) to about 700° F. (about 371° C.); a total pressure from about300 psig (about 2.1 MPag) to about 3000 psig (about 20.7 MPag), forexample from about 700 psig (about 4.8 MPag) to about 2000 psig (about13.8 MPag); an LHSV from about 0.1 hr⁻¹ to about 20 hr⁻¹, for examplefrom about 0.2 hr⁻¹ to about 10 hr⁻¹; and a hydrogen treat gas rate fromabout 500 scf/bbl (about 89 m³/m³) to about 10000 scf/bbl (about 1781m³/m³), for example from about 750 scf/bbl (about 134 m³/m³) to about7000 scf/bbl (about 1247 m³/m³) or from about 1000 scf/bbl (about 178m³/m³) to about 5000 scf/bbl (about 890 m³/m³).

By the term “treat gas”, “hydrogen treat gas” or “hydrogen treat gasstream” as used herein, it is meant a gas stream which can be eitherpure hydrogen or a hydrogen-containing gas, which contains hydrogen inan amount at least sufficient for the intended reaction purpose(s),optionally in addition to one or more other gases (e.g., nitrogen, lighthydrocarbons such as methane, and the like, and combinations thereof)that generally do not adversely interfere with or affect either thereactions or the products. Impurities, such as H₂S, NH₃, CO, and CO₂ aretypically undesirable and would typically be removed from, or reduced todesirably low levels in, the hydrogen treat gas before it is conductedto the reactor bed/zones(s). The treat gas stream introduced into thehydroprocessing reactor can preferably contains at least about 50 vol %hydrogen. However, the treat gas streams utilized herein more preferablycontains at least 75 vol % hydrogen, more preferably at least 85 vol %hydrogen, or even at least 95 vol % hydrogen.

The first reaction zone effluent preferably contains less than 25 wt %,more preferably less than 10 wt % and most preferably less than 5 wt %of organically bound sulfur than exists in the hydrocarbon feedstock. Inpreferred embodiments, first reaction zone effluent contains less than250 ppm, more preferably less than 100 ppm, even more preferably lessthan 50 ppm and most preferably less than 30 ppm of organically boundsulfur. The majority of the organic sulfur content of the hydrocarbonfeedstream is converted into H₂S in this first reactor bed.

The first reaction zone effluent also preferably contains less than 50wt %, more preferably, less than 25 wt % and most preferably less than10 wt % of organically bound oxygen that exists in the hydrocarbonfeedstock. In preferred embodiments, first reaction zone effluentcontains less than less than 10,000 ppm, more preferably less than 5,000ppm, even more preferably less than 1,000 ppm and most preferably lessthan 500 ppm of organically bound oxygen. The majority of the organicoxygen content is converted into H₂O (or “water”, which also may be inthe form of steam) in this first reaction zone. In embodiments, thewater partial pressure in the first reaction zone effluent will begreater than 2 psia, or greater than 5 psia, or in some instances, evengreater than 10 psia under these hydroprocessing conditions and theseconditions will be experienced in the second reaction zone of thehydroprocessing reactor in the processes herein.

Second Reaction Zone

In the processes herein, the first reaction zone effluent is passed tothe second reaction zone without separation of the reaction componentswithin the first reaction zone effluent stream. Additional streams, suchas a second hydrogen treat gas stream, may be added to the firstreaction zone effluent prior to, or simultaneous with, contact of thefirst reaction zone effluent with the catalyst(s) located in the secondreaction zone of the hydroprocessing reactor.

In the processes herein, the second reaction zone contains a catalystoperated under process conditions suitable for catalytic hydrodewaxingthe first reaction zone effluent, which has been derived from a combinedhydrocarbon feedstock comprising both a mineral oil component and abiomass oil component. By the term “catalytic hydrodewaxing” (orconversely “dewaxing”) as utilized herein, it is meant process where ahydrocarbon containing waxy molecules, including n-paraffins whichcontain at least 12 or more carbon atoms (i.e. “C₁₂+” hydrocarbons), areat least partially converted into isomers (i.e., “isomerized”) in thepresence of a catalyst and excess hydrogen. This second reaction zonemay contain multiple catalysts beds. In this second reaction zone, atleast one of these catalyst beds is to be comprised of the “dewaxingcatalyst”, or as may be alternatively referred to herein as the “secondcatalyst”, as further described herein.

A particular problem in dewaxing the resulting first reaction zoneeffluent is the high content of water reactant products present in theresultant effluent from the first reaction zone. As noted prior,conventional dewaxing catalysts, in particular alumina supporteddewaxing catalysts, can be physically unstable, resulting in catalystloss as well as a corresponding decrease in hydroconversionefficiencies.

In order to be effective in the methods according to the invention,dewaxing catalyst compositions utilized in the second reaction zoneshould be capable of hydroisomerization/dewaxing while minimizingphysical catalyst loss and maximizing/maintaining high conversionefficiencies. Optionally, the dewaxing catalyst compositions utilizedaccording to the invention may additionally be capable of at leastpartially hydrocracking the first reactor bed effluent. Thewater-resistant dewaxing catalyst compositions utilized herein comprisea hydrophilic, hydrothermally-stable support such as a zeolitic support,at least one active metal compound comprising one or more of Group VIBmetals and Group VIII metals deposited thereon, and a hydrophilic,hydrothermally-stable binder.

Zeolitic supports according to use in the dewaxing catalysts of thepresent invention can include, but are not limited to crystallinealuminosilicates molecular sieves and/or 1-D or 3-D molecular sieve (forexample, 10-member ring 1-D molecular sieves). Examples of suitabledewaxing catalyst supports can include, but are not limited to,ferrierite, mordenite, ZSM-5, ZSM-22 (also known as theta one or TON),ZSM-23, ZSM-35, ZSM-48, zeolite Beta, zeolite Y, USY, other Group IIA,IVB, VB, and/or VIB oxides, and combinations thereof (for example,molecular sieves such as ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-48, andcombinations thereof, particularly molecular sieves such as ZSM-5,ZSM-48, and/or ZSM-23).

The at least one active metal compound, which typically includes a metalhydrogenation component, can comprise a Group VIII metal. Suitable GroupVIII metals can include Pt, Pd, Ni, Co, or combinations thereof. In someembodiments, the dewaxing catalyst composition can include at least 0.1wt % of the Group VIII metal(s), for example at least about 0.3 wt %, atleast about 0.5 wt %, at least about 1.0 wt %, at least about 2.5 wt %,or at least about 5.0 wt %. Additionally or alternately, the catalystcomposition can include about 10.0 wt % or less of the Group VIIImetal(s), for example about 5.0 wt % or less, about 2.5 wt % or less,about 1.5 wt % or less, or about 1.0 wt % or less.

In some embodiments, the dewaxing catalyst composition can include as anadditional hydrogenation component a Group VIB metal, such as W and/orMo. Typically, the Group VIB metal(s) can be present when the Group VIIImetal(s) comprise(s) a non-noble metal (such as Ni and/or Co). Anexample of such an embodiment could be a dewaxing catalyst compositionthat includes the following metals: NiW, NiMo, or NiMoW. When present,the dewaxing catalyst composition can include at least about 0.5 wt % ofthe Group VIB metal(s), for example at least about 1.0 wt %, at leastabout 2.5 wt %, or at least about 5.0 wt %. Additionally or alternately,the dewaxing catalyst composition can include about 20.0 wt % or less ofthe Group VIB metal(s), for example about 15.0 wt % or less, about 10.0wt % or less, about 5.0 wt % or less, or about 1.0 wt % or less. Wherethe dewaxing catalyst composition contains only Group VIII metals,however, noble Group VIII metals (such as Pt and/or Pd) are thepreferred Group VIII metals.

The binder of the dewaxing catalyst composition, which canadvantageously be hydrophilic and/or hydrothermally-stable, is comprisedof one or more metals selected from titanium, zirconium, vanadium,molybdenum, manganese, and cerium, activated carbon, and/or carbon onwhich is deposited one or more metals selected from titanium, zirconium,vanadium, molybdenum, manganese, and cerium. More preferably, the binderof the dewaxing catalyst is comprised of one or metals selected fromtitanium, zirconium, vanadium, molybdenum, manganese, and cerium. Evenmore preferably, the binder of the dewaxing catalyst is comprised of oneor metals selected from titanium, zirconium, and cerium. Mostpreferably, the binder comprises titanium.

In other embodiments, the binder of the dewaxing catalyst consistsessentially of one or more metals selected from titanium, zirconium,vanadium, molybdenum, manganese, and cerium, activated carbon, and/orcarbon on which is deposited one or more metals selected from titanium,zirconium, vanadium, molybdenum, manganese, and cerium. In anotherembodiment, the binder of the dewaxing catalyst consists essentially ofone or metals selected from titanium, zirconium, vanadium, molybdenum,manganese, and cerium. In another embodiment, the binder of the dewaxingcatalyst consists essentially of one or metals selected from titanium,zirconium, and cerium. In yet another embodiment, the binder consistsessentially of titanium.

The form of the one or more metals may be metallic but typicallycomprises an oxide, carbide, nitride, phosphide, sulfide, or combinationthereof (e.g., a combination of a carbide and nitride could be anitrile; a combination of a phosphide and an oxide could be a phosphate,a phosphite, a hypophosphite, or the like). Preferably, but notnecessarily, the binder comprises titania (aka titanium dioxide). Thedewaxing catalyst compositions according to the present invention mayconsist essentially of the aforementioned components or may optionallycontain additional components, such as sources of other transitionmetals (e.g., Group V metals such as niobium), sources of rare earthmetals, organic ligands (e.g., as added or as precursors left over fromoxidation and/or sulfidization steps), phosphorus compounds, boroncompounds, fluorine-containing compounds, silicon-containing compounds,promoters, additional binders, fillers, or like agents, or combinationsthereof. The Groups referred to herein refer to Groups of the CASVersion as found in the Periodic Table of the Elements in Hawley'sCondensed Chemical Dictionary, 13^(th) Edition.

Preferred conditions in the second reaction zone of the hydroprocessingreactor include contacting the hydrocarbon feedstock and a firsthydrogen treat gas stream with the dewaxing catalyst under secondhydroprocessing conditions sufficient to produce a second reaction zoneeffluent with improved cold flow properties, such as, but not limited toimproved cloud point properties.

These second hydroprocessing conditions can comprise one or more of: aweight average bed temperature (WABT) from about 500° F. (about 260° C.)to about 800° F. (about 427° C.), for example from about 550° F. (about288° C.) to about 700° F. (about 371° C.); a total pressure from about300 psig (about 2.1 MPag) to about 3000 psig (about 20.7 MPag), forexample from about 700 psig (about 4.8 MPag) to about 2000 psig (about13.8 MPag); an LHSV from about 0.1 hr⁻¹ to about 20 hr⁻¹, for examplefrom about 0.2 hr⁻¹ to about 10 hr⁻¹. Excess hydrogen can be added inthe first reaction zone so as to provide excess hydrogen in the firstreactor bed effluent to this second reaction zone. In preferredembodiments, a second hydrogen treat gas may be added to the firstreaction zone effluent prior to, or simultaneously with the contactingof the first reaction zone effluent with the dewaxing catalyst locatedin the second reaction zone. In such case, a second hydrogen treat gasrate from about 200 scf/bbl (about 36 m³/m³) to about 5000 scf/bbl(about 890 m³/m³) is preferred.

The product of this second reaction zone processing is the “secondreaction zone effluent”. This effluent may be further processed byadditional catalyst beds and/or reaction zones in the hydroprocessingreactor, but not to be limiting and simply for the sake of simplicity,we will continue to describe the processes herein in terms of anembodiment wherein only the first reaction zone and second reactionzones and associated catalysts beds are present in the hydroprocessingreactor. In such an embodiment of the invention, the second reactionzone effluent is withdrawn from the hydroprocessing reactor. Preferablyat least a portion of the second reaction zone effluent is separated toform a gas phase product and a reactor effluent product. Additionally oroptionally, the reaction zone effluent is withdrawn from thehydroprocessing reactor and sent to a fractionator tower wherein the gasphase product is removed from the reactor effluent product and thereactor effluent product is simultaneously fractionated into two or moredifferent boiling range liquid product streams. In this latterembodiment, the term “reactor effluent product” is considered to be thecombination of the liquid product streams fractionated unless otherwisedesignated as, or referred to as, a particular fraction of the overallreactor effluent product herein. By the term “liquid product” or “liquidproduct stream” as utilized in the context herein, it is meant thereactor product components of the present processes which are a liquidat standard (atmospheric) pressure and temperature.

FIG. 1 shows a simplified schematic of an embodiment of the processconfiguration herein wherein a single reactor is utilized with only two(2) reaction zones as have been described herein. FIG. 1 also shows theoptional use of a flash drum to separate the gas phase products from thesecond reaction zone effluent in order to form a reactor effluentproduct which can be further separated for motor fuel use.

In FIG. 1, a mineral oil component 1 and a biomass oil component 5 arecombined to form a combined hydrocarbon feedstock 10. Although suchcombination is illustrated in the figure as occurring just prior toentering the hydroprocessing reactor 20 for simplicity, the invention isnot so limited. Typically, the two component streams will be mixed in aportion of the process significantly prior to introduction into thehydroprocessing reactor 20. The combined streams may additional undergopre-processing prior to the step of the processes as illustrated in FIG.1.

Continuing with FIG. 1, the combined hydrocarbon feedstock 10 (or simplyreferred to as the “hydrocarbon feedstock” herein) enters thehydroprocessing reactor 20. A first hydrogen treat gas stream 15 iscombined with the hydrocarbon feedstock. In FIG. 1, this combining isshown as mixing with the hydrocarbon feedstock stream 10 prior to entryinto the reactor. However, the first hydrogen treat gas stream 15 may beintroduced into the processes herein optionally, or additionally,directly into the hydroprocessing reactor 20. The hydrogen feedstock 10and first hydrogen treat gas 15 contact the catalyst(s) in the firstreactor zone 25 under first hydroprocessing conditions as have beendescribed herein. The first reaction zone 25 contains ahydrodesulfurization/deoxygenation catalyst as has been described in thedetails of the invention herein. The combined stream components passthrough the catalyst(s) in the first reaction zone 25 where thecomponents are catalytically converted into different molecular productsand emerge from the first reaction zone as a first reaction zoneeffluent (not separately designated in the figure) which then passes tothe second reaction zone 30 under second hydroprocessing conditions ashave been described herein. Optionally, a second hydrogen treat gasstream 35 can be added to the process prior to the second reaction zone30 as shown. The first reaction zone effluent is catalytically convertedin the second reaction zone 30 to produce the product properties asdescribed in the detailed description herein and can be withdrawn fromthe hydroprocessing reactor 20 as a second reaction zone effluent 40 asshown.

In the embodiment shown in FIG. 1, a flash drum 50 is utilized toseparate the second reaction zone effluent 40 into gas phase products 55and a reactor effluent product 60. Although not shown, the secondreaction zone effluent 40 may undergo additional cooling prior toentering the flash drum 50. The reactor effluent product 60 can then befurther processed and/or separated into fractions for use in diesel,kerosene, jet, heating oil, marine, bunker fuels, and/or lubes.

FIG. 2 illustrates another optional embodiment of the processes herein.In this configuration, elements/processes 1 through 40 as were describedin FIG. 1 are essentially the same as shown in FIG. 2. However, since apreferred use of the processes herein are to produce at least on motorfuel product stream, such as a naphtha stream (for gasoline blending) ordistillate (for diesel blending) which meet motor fuel specificationswhile co-processing a combined mineral oil/biomass component stream, afractionator tower 70 is utilized to directly separate the secondreaction zone effluent 40 into useable motor fuel fractions.

Here the second reaction zone effluent 40 is shown entering afractionator tower 70 and being split into various product streams.Here, a gas phase stream 75 is withdrawn from the overhead of thefractionation tower 70. It should be noted that an option (notshown/detailed in FIG. 2) would also be to utilize a flash drum (asshown as element 50 in FIG. 1) to make an initial separation of thesecond reaction zone effluent 40 into a gas stream and liquid stream andthen the liquid stream could be passed to the fractionator tower 70 forfurther separation as will be further described. Continuing with theconfiguration shown in FIG. 2, gas phase stream 75 will primarilycontain some hydrogen, incondensable products from the reaction process(such as hydrogen sulfide), water, and light petroleum gases or “LPGs”(such as propane and butane).

In preferred embodiments herein are least one, or both of, a naphtharange fraction 80 having a boiling range between 80° F. (27° C.) and450° F. (232° C.) and/or a distillate range fraction 85 having a boilingrange between 400° F. (204° C.) and 700° F. (371° C.) are drawn from thefractionator tower 70. As described herein, these products will haveimproved product qualities for use in motor fuels. For instance, thenaphtha range fraction will have lower sulfur than the hydrocarbon feedintroduced to the process and preferably will be low enough in sulfur tomeet motor gasoline specifications. The naphtha range fraction shouldalso be improved in isomer content which will improve gasoline octane.Similarly, the resultant distillate product will have improved productqualities for use in a diesel motor fuel. The distillate range fractionwill have lower sulfur than the hydrocarbon feed introduced to theprocess and preferably will be low enough in sulfur to meet motor dieselspecifications. The distillate fraction will also have improved cloudpoint properties over the unprocessed distillate fraction of thecombined hydrocarbon feedstock, and will preferably meet the commercialtransportation and use specifications for diesel motor fuels withoutfurther conversion processing.

Continuing with FIG. 2, optionally, if the hydrocarbon feedstockcontains fractional components with boiling points significantly higherthan distillate boiling ranges, a marine/bunker fuel fraction 90 can bewithdrawn from the fractionation tower 70. Additionally, in such cases,a lube oil fraction 95 may also be withdrawn from the fractionationtower 70. The processes of invention herein are exceptionally useful inproducing a low sulfur lube oil fraction with improved pour point andviscosity properties.

In preferred embodiments, the reactor effluent product will have abranched (iso-) paraffin content that is at least 10 wt % higher, andmore preferably at least 20 wt % higher, and even more preferably atleast 35 wt % higher than the branched (iso-) paraffin content of thecombined hydrocarbon feedstock.

Additionally, in preferred embodiments herein, after separation of thegas phase stream from the second reaction zone effluent stream, thereactor effluent product stream preferably contains less than 25 wt %,more preferably less than 10 wt % and most preferably less than 5 wt %of the sulfur that is present in the hydrocarbon feedstock. In preferredembodiments, the reactor effluent product stream contains less than 250ppm, more preferably less than 100 ppm, even more preferably less than50 ppm and most preferably less than 30 ppm of sulfur.

Additionally, in preferred embodiments herein, after separation of thegas phase stream from the second reaction zone effluent stream, thereactor effluent product stream preferably contains less than 50 wt %,more preferably, less than 25 wt % and most preferably less than 10 wt %of the oxygen that is present in the hydrocarbon feedstock. In preferredembodiments, reactor effluent product stream contains less than lessthan 10,000 ppm, more preferably less than 5,000 ppm, even morepreferably less than 1,000 ppm and most preferably less than 500 ppmoxygen.

In some embodiments, one or more portions of the reactor effluentproduct (or perhaps even the entire product) of the methods according tothe present invention can advantageously be used as one or moretransportation fuel compositions and/or may be sent to one or moreexisting fuel pools. Non-limiting examples of such fuelcompositions/pools can include, but are not limited to, diesel,kerosene, jet, heating oil, marine, and/or bunker fuels. For instance,in one embodiment, the distillate portion(s) of the product can be split(e.g., by fractionation or the like) into a kerosene cut having aboiling range between 400° F. (204° C.) and 550° F. (288° C.) and adiesel cut having a boiling range between 550° F. (232° C.) and 700° F.(371° C.).

In more preferred embodiments, a diesel boiling range fraction of thereactor effluent product is separated/isolated, and the diesel boilingrange fraction can exhibit a cloud point that is less than 0° C.,preferably less than −5° C., or less than −10° C., or less than −15° C.,or less than −20° C., or less than −25° C., or less than −30° C., orless than −35° C., or less than −40° C.

Additionally or alternately, the present invention can include thefollowing embodiments.

Embodiment 1

A method for processing a hydrocarbon feedstock comprised of a mineraloil component and a biomass oil component to form at least one liquidmotor fuel product, such method comprising:

a) contacting the hydrocarbon feedstock and a first hydrogen treat gasstream with a hydrodesulfurization/deoxygenation catalyst in a firstreaction zone of a hydroprocessing reactor under first hydroprocessingconditions sufficient to produce a first reaction zone effluent whichcontains less organically bound sulfur than the hydrocarbon feedstockand less organically bound oxygen than the hydrocarbon feedstock;

b) contacting the first reaction zone effluent with a dewaxing catalystin a second reaction zone of the hydroprocessing reactor under secondhydroprocessing conditions sufficient to produce a second reaction zoneeffluent;

c) separating a gas phase product stream from the second reaction zoneeffluent to produce a reactor effluent product which has a lower sulfurcontent and a lower oxygen content than the hydrocarbon feedstock; and

d) producing at least one liquid motor fuel product from at least aportion of the reactor effluent product;

wherein the dewaxing catalyst comprises a zeolitic support, at least oneactive metal compound comprising one or more of Group VIB metals andGroup VIII metals deposited thereon, and a hydrophilic,hydrothermally-stable binder comprising one or more of: (A) an oxide,carbide, nitride, phosphide, sulfide, or combination thereof of one ormore metals selected from titanium, zirconium, vanadium, molybdenum,manganese, and cerium, (B) activated carbon, and (C) carbon on which isdeposited one or more metals selected from titanium, zirconium,vanadium, molybdenum, manganese, and cerium.

Embodiment 2

The method of embodiment 1, wherein the binder of the dewaxing catalystcomprises zirconia, vanadia, titania, molybdenum oxide, manganese oxide,cerium oxide, carbon, or a combination thereof.

Embodiment 3

The method of embodiment 1, wherein the binder of the dewaxing catalystcomprises one or metals selected from titanium, zirconium, vanadium,molybdenum, manganese, and cerium.

Embodiment 4

The method of embodiment 3, wherein the binder of the dewaxing catalystcomprises one or metals selected from titanium, zirconium, and cerium.

Embodiment 5

The method of embodiment 4, wherein the binder of the dewaxing catalystconsists essentially of one or metals selected from titanium, zirconium,and cerium.

Embodiment 6

The method of embodiment 3, wherein the binder of the dewaxing catalystcomprises titanium.

Embodiment 7

The method of embodiment 6, wherein the binder of the dewaxing catalystconsists essentially of titanium.

Embodiment 8

The method of any prior embodiment, wherein the zeolitic support of thedewaxing catalyst comprises ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-48,zeolite Beta, zeolite Y, USY, mordenite, ferrierite, or a combinationthereof.

Embodiment 9

The method of any prior embodiment, wherein thehydrodesulfurization/deoxygenation catalyst comprises at least one GroupVIII metal oxide selected from Fe, Co and Ni, and at least one Group VIBmetal oxide selected from Mo and W.

Embodiment 10

The method of any prior embodiment, wherein thehydrodesulfurization/deoxygenation catalyst further comprises a supportselected from alumina, silica, and silica-alumina.

Embodiment 11

The method of any prior embodiment, wherein the first hydroprocessingconditions include one or more of: a weight average bed temperature(WABT) from about 500° F. (about 260° C.) to about 800° F. (about 427°C.); a total pressure from about 300 psig (about 2.1 MPag) to about 3000psig (about 20.7 MPag); an LHSV from about 0.1 hr⁻¹ to about 20 hr⁻¹;and a hydrogen treat gas rate from about 500 scf/bbl (about 89 m³/m³) toabout 10000 scf/bbl (about 1781 m³/m³).

Embodiment 12

The method of any prior embodiment, wherein the water partial pressurein the first reaction zone effluent is greater than 2 psia.

Embodiment 13

The method of any prior embodiment, wherein the second hydroprocessingconditions include one or more of: a weight average bed temperature(WABT) from about 500° F. (about 260° C.) to about 800° F. (about 427°C.); a total pressure from about 300 psig (about 2.1 MPag) to about 3000psig (about 20.7 MPag); an LHSV from about 0.1 hr⁻¹ to about 20 hr⁻¹.

Embodiment 14

The method of any prior embodiment, wherein the second hydroprocessingconditions further include a water partial pressure of greater than 5psia.

Embodiment 15

The method of any prior embodiment, wherein the second hydroprocessingconditions include the introduction of a second hydrogen treat gas at atreat gas rate from about 200 scf/bbl (about 36 m³/m³) to about 5000scf/bbl (about 890 m³/m³).

Embodiment 16

The method of any prior embodiment, wherein the second reaction zoneeffluent is separated in a flash drum to produce the gas phase productstream and the reactor effluent product.

Embodiment 17

The method of any one of embodiments 1-15, wherein the second reactionzone effluent is separated in a fractionator tower to produce the gasphase product stream and the reactor effluent product.

Embodiment 18

The method of any prior embodiment, wherein the hydrocarbon feedstockcontains from 80 wt % to about 98 wt % of the mineral oil component andfrom 2 wt % to about 20 wt % of the biomass oil component, the mineraloil component contains at least 500 ppmw sulfur, and the reactoreffluent product contains less than 100 ppmw sulfur.

Embodiment 19

The method of embodiment 18, wherein the biomass oil component containsat least 2 wt % oxygen, and the reactor effluent product contains lessthan 1,000 ppmw oxygen.

Embodiment 20

The method of any prior embodiment, wherein the biomass oil component isderived from algae.

Embodiment 21

The method of any prior embodiment, wherein the hydrocarbon feedstockhas an T5 boiling point of at least about 200° F. (93° C.) and a T95boiling point of less than about 800° F. (427° C.).

Embodiment 22

The method of any prior embodiment, wherein the at least one liquidmotor fuel product is produced from a diesel boiling range fraction ofthe reactor effluent product wherein the cloud point of the dieselboiling range fraction is less than 0° C.

Embodiment 23

The method of any prior embodiment, wherein the reactor effluent producthas a branched (iso-) paraffin content that is at least 20 wt % higherthan the branched (iso-) paraffin content of the hydrocarbon feedstock.

Embodiment 24

The method of any one of embodiments 1 and 8-23, wherein the dewaxingcatalyst is comprised of ZSM-48, and a Group VIII metal selected frompalladium and platinum with a metal content from about 0.1 wt % to about3.0 wt % based on the weight of the ZSM-48, and a titania binder.

Embodiment 25

The method of any one of embodiments 1 and 8-23, wherein the dewaxingcatalyst is comprised of ZSM-48, a Group VIII non-noble metal selectedfrom nickel, cobalt, and iron with a Group VIII metals content fromabout 0.5 wt % to about 20 wt % based on the weight of the ZSM-48, aGroup VIB metal selected from molybdenum and tungsten with a Group VIBmetals content from about 3 wt % to about 25 wt %, based on the weightof the ZSM-48, and a titania binder.

Embodiment 26

The method of any one of embodiments 17-25, wherein a naphtha boilingrange fraction and a distillate boiling range fraction are drawn fromthe fractionator tower.

Embodiment 27

The method of embodiment 26, wherein the naphtha boiling range fractionfrom the fraction tower has a higher octane value than the naphthaboiling range fraction of the hydrocarbon feedstock.

Embodiment 28

The method of any one of embodiments 26-27, wherein the distillateboiling range fraction from the fraction tower has a lower cloud pointand a lower pour point than the distillate boiling range fraction of thehydrocarbon feedstock.

Embodiment 29

The method of any one of embodiments 26-28, wherein the distillateboiling range fraction contains a diesel boiling range fraction with acloud point of less than 0° C.

EXAMPLES

The examples herein illustrate the properties of the water tolerantcatalysts herein to shown higher and maintain conversion activity overcomparable catalysts of the prior art in aqueous phase hydroconversionprocessing.

Example 1

Stearic acid feed was converted over a series of different catalystcompositions and at temperatures of about 250° C., about 275° C., about300° C., and about 325° C. These catalyst compositions included <1 wt %Pt on alumina support/binder, <1 wt % Pt on ZSM-23 support (total metalon support was about 65% of catalyst weight) with titania binder (about35% of catalyst weight), <1 wt % Pt on ZSM-48 support (total metal onsupport was about 65% of catalyst weight) with alumina binder (about 35%of catalyst weight), <1 wt % Pt on ZSM-48 support with titania binder,<1 wt % Pt on ZSM-5 support (total metal on support was about 65% ofcatalyst weight) with alumina binder (about 35% of catalyst weight), andZSM-5 with no metal and no binder. At all temperatures tested,titania-containing (or, more broadly, non-alumina-containing) catalystcompositions exhibited higher conversion of the stearic acid feed thanalumina-containing catalyst compositions. At about 275° C. and above,the titania-(non-alumina-) containing catalysts all exhibited conversionlevels of at least 15% (for example from about 20% to about 95%),whereas alumina-containing catalysts exhibited conversion levels below10%. These conversion levels were based on calculations involving massbalances, which can also be a good indicator for the oxygen content. Asdeoxygenation can occur via decarboxylation and dehydration, assumingcomplete loss of the formed CO₂ and water at the reaction/processingconditions, conversion levels (at least for thedecarbonylation/decarboxylation reaction) can tend to increase withdecreasing mass balance. Catalysts with binders that are not hydrophilicand/or not hydrothermally stable, such as alumina-containing catalysts,show very low activity for deoxygenation of such feeds.

Example 2

In Example 2, a direct comparison was made between the activity of twocatalyst compositions that were identical, except for the binder. Thefirst catalyst composition was <1 wt % Pt on ZSM-48 support with analumina binder, whereas the second catalyst composition was <1 wt % Pton ZSM-48 support with a titania binder. Stearic acid feed was convertedover each catalyst at a temperature of about 325° C., with a weighthourly space velocity of about 0.3 hr⁻¹, and under a hydrogen partialpressure of about 400 psig (about 2.8 MPag). The product was analyzedusing a gas chromatograph linked to a mass spectrometer (GC-MS). Thespectral comparison is shown in FIG. 3, with the titania binder at thetop and the alumina binder at the bottom. The catalyst compositioncontaining the titania binder showed substantially complete conversionof the feed from paraffin to branched (iso-) paraffin, withsubstantially complete deoxygenation as well. The pour point of this topsample was determined to be below about −50° C., based on analysis viadifferential scanning calorimetry (DSC), using a temperature rate ofchange of approximately 10° C./minute. The catalyst compositioncontaining the alumina binder showed large amounts of unconvertedstearic acid, with some limited deoxygenation but with only barelydetectable (trace) amounts of conversion from paraffin to branched(iso-) paraffin. The pour point of this bottom sample was determined tobe about +52° C., based on DSC analysis. For comparison, the pour point(melting point) of the stearic acid feed was about +69° C.

The principles and modes of operation of this invention have beendescribed above with reference to various exemplary and preferredembodiments. As understood by those of skill in the art, the overallinvention, as defined by the claims, encompasses other preferredembodiments not specifically enumerated herein.

What is claimed is:
 1. A method for processing a hydrocarbon feedstockcomprised of a mineral oil component and a biomass oil component to format least one liquid motor fuel product, such method comprising: a)contacting the hydrocarbon feedstock and a first hydrogen treat gasstream with a hydrodesulfurization/deoxygenation catalyst in a firstreaction zone of a hydroprocessing reactor under first hydroprocessingconditions sufficient to produce a first reaction zone effluent whichcontains less organically bound sulfur than the hydrocarbon feedstockand less organically bound oxygen than the hydrocarbon feedstock; b)contacting the first reaction zone effluent with a dewaxing catalyst ina second reaction zone of the hydroprocessing reactor under secondhydroprocessing conditions sufficient to produce a second reaction zoneeffluent; c) separating a gas phase product stream from the secondreaction zone effluent to produce a reactor effluent product which has alower sulfur content and a lower oxygen content than the hydrocarbonfeedstock; and d) producing at least one liquid motor fuel product fromat least a portion of the reactor effluent product; wherein the dewaxingcatalyst comprises a zeolitic support, at least one active metalcompound comprising one or more of Group VIB metals and Group VIIImetals deposited thereon, and a hydrophilic, hydrothermally-stablebinder comprising one or more of: (A) an oxide, carbide, nitride,phosphide, sulfide, or combination thereof of one or more metalsselected from titanium, zirconium, vanadium, molybdenum, manganese, andcerium, (B) activated carbon, and (C) carbon on which is deposited oneor more metals selected from titanium, zirconium, vanadium, molybdenum,manganese, and cerium.
 2. The method of claim 1, wherein the binder ofthe dewaxing catalyst comprises zirconia, vanadia, titania, molybdenumoxide, manganese oxide, cerium oxide, carbon, or a combination thereof.3. The method of claim 1, wherein the binder of the dewaxing catalystcomprises one or metals selected from titanium, zirconium, vanadium,molybdenum, manganese, and cerium.
 4. The method of claim 3, wherein thebinder of the dewaxing catalyst comprises one or metals selected fromtitanium, zirconium, and cerium.
 5. The method of claim 4, wherein thebinder of the dewaxing catalyst consists essentially of one or metalsselected from titanium, zirconium, and cerium.
 6. The method of claim 3,wherein the binder of the dewaxing catalyst comprises titanium.
 7. Themethod of claim 6, wherein the binder of the dewaxing catalyst consistsessentially of titanium.
 8. The method of claim 1, wherein the zeoliticsupport of the dewaxing catalyst comprises ZSM-5, ZSM-22, ZSM-23,ZSM-35, ZSM-48, zeolite Beta, zeolite Y, USY, mordenite, ferrierite, ora combination thereof.
 9. The method of claim 1, wherein thehydrodesulfurization/deoxygenation catalyst comprises at least one GroupVIII metal oxide selected from Fe, Co and Ni, and at least one Group VIBmetal oxide selected from Mo and W.
 10. The method of claim 9, whereinthe hydrodesulfurization/deoxygenation catalyst further comprises asupport selected from alumina, silica, and silica-alumina.
 11. Themethod of claim 10, wherein the first hydroprocessing conditions includeone or more of: a weight average bed temperature (WABT) from about 500°F. (about 260° C.) to about 800° F. (about 427° C.); a total pressurefrom about 300 psig (about 2.1 MPag) to about 3000 psig (about 20.7MPag); an LHSV from about 0.1 hr⁻¹ to about 20 hr⁻¹; and a hydrogentreat gas rate from about 500 scf/bbl (about 89 m³/m³) to about 10000scf/bbl (about 1781 m³/m³).
 12. The method of claim 11, wherein thewater partial pressure in the first reaction zone effluent is greaterthan 2 psia.
 13. The method of claim 11, wherein the secondhydroprocessing conditions include one or more of: a weight average bedtemperature (WABT) from about 500° F. (about 260° C.) to about 800° F.(about 427° C.); a total pressure from about 300 psig (about 2.1 MPag)to about 3000 psig (about 20.7 MPag); an LHSV from about 0.1 hr⁻¹ toabout 20 hr⁻¹.
 14. The method of claim 13, wherein the secondhydroprocessing conditions further include a water partial pressure ofgreater than 5 psia.
 15. The method of claim 14, wherein the secondhydroprocessing conditions include the introduction of a second hydrogentreat gas at a treat gas rate from about 200 scf/bbl (about 36 m³/m³) toabout 5000 scf/bbl (about 890 m³/m³).
 16. The method of claim 1, whereinthe second reaction zone effluent is separated in a flash drum toproduce the gas phase product stream and the reactor effluent product.17. The method of claim 1, wherein the second reaction zone effluent isseparated in a fractionator tower to produce the gas phase productstream and the reactor effluent product.
 18. The method of claim 1,wherein the hydrocarbon feedstock contains from 80 wt % to about 98 wt %of the mineral oil component and from 2 wt % to about 20 wt % of thebiomass oil component, the mineral oil component contains at least 500ppmw sulfur, and the reactor effluent product contains less than 100ppmw sulfur.
 19. The method of claim 18, wherein the biomass oilcomponent contains at least 2 wt % oxygen, and the reactor effluentproduct contains less than 1,000 ppmw oxygen.
 20. The method of claim19, wherein the biomass oil component is derived from algae.
 21. Themethod of claim 1, wherein the hydrocarbon feedstock has an T5 boilingpoint of at least about 200° F. (93° C.) and a T95 boiling point of lessthan about 800° F. (427° C.).
 22. The method of claim 1, wherein the atleast one liquid motor fuel product is produced from a diesel boilingrange fraction of the reactor effluent product wherein the cloud pointof the diesel boiling range fraction is less than 0° C.
 23. The methodof claim 17, wherein the at least one liquid motor fuel product isproduced from a diesel boiling range fraction of the reactor effluentproduct wherein the cloud point of the diesel boiling range fraction isless than 0° C.
 24. The method of claim 22, wherein the reactor effluentproduct has a branched (iso-) paraffin content that is at least 20 wt %higher than the branched (iso-) paraffin content of the hydrocarbonfeedstock.
 25. The method of claim 1, wherein the dewaxing catalyst iscomprised of ZSM-48, and a Group VIII metal selected from palladium andplatinum with a metal content from about 0.1 wt % to about 3.0 wt %based on the weight of the ZSM-48, and a titania binder.
 26. The methodof claim 1, wherein the dewaxing catalyst is comprised of ZSM-48, aGroup VIII non-noble metal selected from nickel, cobalt, and iron with aGroup VIII metals content from about 0.5 wt % to about 20 wt % based onthe weight of the ZSM-48, a Group VIB metal selected from molybdenum andtungsten with a Group VIB metals content from about 3 wt % to about 25wt %, based on the weight of the ZSM-48, and a titania binder.
 27. Themethod of claim 17, wherein a naphtha boiling range fraction and adistillate boiling range fraction are drawn from the fractionator tower.28. The method of claim 27, wherein the naphtha boiling range fractionfrom the fraction tower has a higher octane value than the naphthaboiling range fraction of the hydrocarbon feedstock.
 29. The method ofclaim 28, wherein the distillate boiling range fraction from thefraction tower has a lower cloud point and a lower pour point than thedistillate boiling range fraction of the hydrocarbon feedstock.
 30. Themethod of claim 29, wherein the distillate boiling range fractioncontains a diesel boiling range fraction with a cloud point of less than0° C.